This invention relates to a new type of additive for polymer film production, and especially a granulate which contains
a) one or more additives for polymer film production and
b) a micronized silicic acid or an aluminosilicate.
This granulate is suitable as an additive for example in the processing of polyolefins and the production of polyolefin films.
It is known that in the production of polyolefin films several additives are necessary to benefit the various properties of the finished films. They are for example
i) antiblocking agents, for example, fine-particle diatomaceous earth, silicic acid, silica gel;
ii) lubricants, such as for example fatty acid amides and especially oleic acid amide and erucic acid amide;
iii) primary antioxidants from the group of sterically hindered phenols, secondary aryl amines, etc.;
iv) secondary antioxidants from the group of phosphorus compositions, thioesters, hydroxylamines, etc.;
v) antistatic agents from the group of ammonium salts, glycerin esters, anionic compounds, etc.;
vi) light stabilizers from the group of benzophenones, benzotriazols, xe2x80x9cHALSxe2x80x9d (xe2x80x9cSterically Hindered Amines Light Stabilizersxe2x80x9d), etc.;
vii) flame retardants from the group of halogenated organic compounds, metal hydrates, etc.;
viii) softeners from the group of phthalates, monocarboxylic acid esters, aliphatic dicarboxylic acid esters, etc.
Granulates of pure organic additives are already known. At the same time combinations of micronized silicic acids or aluminosilicates as antiblocking agents with organic additives cause poor dispersability when granulation processes according to the prior art are used, for example, compacting in molds or compacting by nozzles (cold pressing).
Japanese patent HEI 569865 for example describes an additive-pellet composition which comprises spherical pellets of amorphous silicoaluminate and organic additives. Organic components can be for example lubricants, antistatic agents and softeners, UV stabilizers and antioxidants, etc. This patent application however is not concerned with synthetic, amorphous silicic acids or with crystalline aluminosilicates.
German patent 33 37 356 describes a combined antiblocking and lubricant concentrate, a master batch being formed with a polyolefin.
German patent 44 24 775 describes a special antiblocking agent based on silicon dioxide with a bimodal pore size distribution. This antiblocking agent is combined with lubricants such as oleic acid amid or erucic acid amide to produce polyolefin master batches.
U.S. Pat. No. 5,053,444 describes a polymer concentrate which contains as the additive aluminum oxide or silicon dioxide. Other additives are lubricants, antioxidants, UV stabilizers, antistatic agents, etc.
All these patents show that so far there has been no success in producing a free-flowing granulate which contains only synthetic, amorphous silicic acid and organic additives and which at the same time can be easily dispersed in polymers. A certain polymer for forming a master batch is always contained. This means that the additive concentrates cannot be used for just any polymer types.
U.S. Pat. No. 3 266 924 describes production of homogenous mixtures of fine particle silicic acid and fatty acid amides in a mixer. The amides are added to the silicic acid during mixing at a temperature near the melting point of the amides. This yields a powder mixture.
In view of the described defects of known additives, the object was to produce an additive that is universally suitable for many applications and polymers, which can be easily and economically used, and thus has application advantages such as good dispersability with simultaneous occurrence in granulate form.
As claimed in the invention, this object was achieved by a granulate composition which is characterized in that it
a) consists of micronized silicic acid gel (A) with an average particle size from 2 to 15 microns, preferably 5 to 10 microns, a specific pore volume from 0.3 to 2.0 ml/g, preferably 0.5 to 1.5 ml/g, a specific surface (BET) from 200 to 1000 m2/g, preferably 200 to 800 m2/g, in a concentration from 5 to 60% by weight, preferably 10 to 50% by weight, especially 15 to 45% by weight, or
b) a hydrated or dehydrated aluminosilicate (B) which contains sodium and/or potassium and/or calcium cations, with an average particle size between 1 and 25 microns in a concentration from 5 to 75% by weight, preferably 10 to 60% by weight, especially 15 to 50% by weight, and
c) an organic additive composition (C) in a concentration from 25 to 95% by weight, preferably 40 to 90% by weight, especially 50 to 85% by weight, but at least 5% more (measured by the oil adsorption process) than that which is necessary to fill all the pores of the silicic acid and the spaces between the silicic acid particles and the aluminosilicate particles.
The composition as claimed in the invention has a dispersability in polymers which is as good as the individual components. The organic composition (C) can consist of one or more of the following components in any proportion:
i) lubricants from the croup of fatty acid amides;
ii) primary antioxidants from the group of sterically hindered phenols, secondary aryl amines, etc.;
iii) secondary antioxidants from the group of phosphorus compositions, thioesters, hydroxylamines, etc.;
iv) antistatic agents from the group of ammonium salts, glycerin esters, anionic compounds, etc.;
v) light stabilizers from the group of benzophenones, benzotriazols, xe2x80x9cHALSxe2x80x9d (xe2x80x9cSterically Hindered Amines Light Stabilizersxe2x80x9d), etc.;
vi) flame retardants from the group of halogenated organic compounds, metal hydrates, etc.;
vii) softeners from the group of phthalates, monocarboxylic acid esters, aliphatic dicarboxylic acid esters, etc.
It has now been surprisingly found that granulates with micronized silicic acid or aluminosilicates lead to good dispersability, if the inorganic components are added to a melt of the organic additives. This can be done by adding the inorganic components to a melt of the organic components produced beforehand or when a premixture of the organic and inorganic components is heated to the melting point of the organic component. The concentration of inorganic components cannot be higher than the critical pigment volume concentration, i.e. the molten organic phase must be able to fill all empty pores of the silicic acid (in the case of aluminosilicate the particle pores are too small for the organic molecules) and the interstices between the organic particles. It is necessary to have an excess of organic components to achieve a paste or liquid mass. The formation of granulates (pellets) is achieved either by spray drying of the melt or by extrusion of strands with subsequent comminution. The preferred technical approach is to use an extruder to melt the organic components and to achieve distribution of inorganic particles. The discharge of the extruder in the form of strands is cut with a means of the prior art (xe2x80x9chot knock-offxe2x80x9d). Afterwards the granulate can be cooled, preferably in a fluidized bed, to prevent aggregation of the individual particles. Another possibility is that the strands are guided into a water bath and cut therein. The surface water is then removed preferably in a fluidized bed.
The advantages of this invention are:
Delivery of all additives in pelletized form with only proportioning into the extruder.
More precise proportioning of the components.
Processing in the final application does not cause any dust.
Higher bulk density of the pellets than those of the simple physical mixtures of amorphous silicic acids and additives (and therefore lower transport and production costs).
Good dispersability of additives in the polymer mass.